Comparative studies on Y(Ⅲ)and Dy(Ⅲ)extraction from hydrochloric and nitric acids by Cyanex 572 as a novel extractant

Extraction of Y(III) and Dy(III) from hydrochloric and nitric acids by Cy-572 in kerosene was studied. The factors affecting the extraction were separately investigated. The stoichiometry of the extracted species was deduced on the basis of slope analysis method. Evaluation of extraction equilibrium and stripping investigation was studied as well as saponification effect of Cy-572. The composition of the extracted metal species in the organic phase was found to be [MA_3·(HA)_3] for Y(III) or Dy(III) in both media.1.0 mol/L HCI is the best stripping agent for each metal ion from the studied acidic media in one step.Saponified Cy-572 does not exhibit any selectivity towards the extraction of Y(III) or Dy(III) from both HCI and HNO_3 solutions. Based on the obtained results, the data were compared and the separation feasibility between lanthanides and Y(III) in the two media was discussed.     

Studies on synergistic solvent extraction of rare earth elements from nitrate medium by mixtures of 8-hydroxyquinoline with Cyanex 301 or Cyanex 302

Synergistic solvent extraction of rare earth elements (REEs) from nitrate medium was investigated with mixtures of 8-hydroxyquinoline (HQ) and acidic organophosphorus extractants,bis(2,4,4-trimethylpentyl) dithiophosphinic acid (Cyanex 301) and bis(2,4,4-trimethylpentyl) monothiophosphinic acid (Cyanex 302).The extraction behavior of Cyanex 301/Cyanex 302 and their binary mixtures with HQ towards several lanthanoids (La,Nd,Sm,Tb,Ho,Tm) and yttrium (Y) was investigated.The separation ability of REEs was studied according to the various extraction effects.The extraction mechanisms for yttrium were studied with the methods of slope analysis and constant moles in the synergistic systems.The extracted compounds,the equilibrium constants,and thermodynamic functions were also determined.     

Study on a novel flat renewal supported liquid membrane with D2EHPA and hydrogen nitrate for neodymium extraction

The Nd(III) extraction in flat renewal supported liquid membrane(FRSLM),with polyvinylidene fluoride membrane and renewal solution including HNO3 solution as the stripping solution and di(2-ethylhexyl) phosphoric acid(D2EHPA) dissolved in kerosene as the membrane solution,was investigated.The effects of pH in the feed phase,volume ratio of membrane solution to stripping solution,concentra-tion of HNO3 solution and concentration of carrier in the renewal phase on extraction of Nd(III) were also studied,respectively.As a result,the optimum extraction conditions of Nd(III) were obtained when concentration of HNO3 solution was 4.00 mol/L,concentration of D2EHPA was 0.100 mol/L,and volume ratio of membrane solution to stripping solution was 1.00 in the renewal phase,and pH was 4.60 in the feed phase.When initial concentration of Nd(III) was 2.00×10-4 mol/L,the extraction percentage of Nd(III) was up to 92.9% in 75 min.     

Phase Formation and Magnetic Properties of Nanocomposite Nd-Fe-B Adjusted by Small Amount of Dy and Co

In order to improve and stabilize the magnetic properties of nanocomposite Nd2Fe14B/α-Fe magnetic alloys by a compositional adjustment, small amount of Dy and/or Co was added to Nd9Fe84B7 alloys. DTA analysis on the amorphous of the alloys took place as the soft magnetic phases were crystallized, and then the hard magnetic Nd2Fe14B was precipitated from them. While α-Fe and a metastable 1:7 (TbCu7-type) phase were formed simultaneously in Dy and Co-free alloys, they were crystallized separately at different temperatures after Dy or Co was added. This phase separation occurred more clearly in the Dy-treated alloys and the other soft magnetic phase Fe3B was also stabilized by Dy and/or Co. The 1: 7 phase that was stabilized by Dy and/or Co was not eliminated at 700 ℃, decreasing magnetic properties of the alloys. It was eventually disappeared above 725 ℃, but Fe3B was not eliminated even at 750 ℃ when Dy was added more than 0.5 at% or Co was added more than 2.0 at%. Amount of Nd2Fe14B in the alloys tended to increase as Dy addition increased,whereas Co addition did not lead to any appreciable change in the ratio of α-Fe and Nd2Fe14B. Moreover, Dy addition apparently increased coercivity of an alloy while Co addition had a beneficial effect on remanence. The grains in the Dytreated alloys were usually finer than those in the Co-treated alloys. The grain size of both α-Fe and Nd2Fe14B in the alloys exhibiting mr ≥ 0.72 was in the range of 20 ～ 40 nm or even larger 50 nm, which is larger than the theoretical optimum size ( ～ 10 nm). Typical magnetic properties obtained from a Nd7.5Dy1.5Fe82.5Co1.5B7 alloy annealed for 12 min at 725 ℃were iHc=4.85 kOe, Br= 11.32 kG, (BH)max = 15.73 MGOe, and mr=0.73.     

Thermodynamics and kinetics of lutetium extraction with HEH(EHP) in hydrochloric acid medium

Solvent extraction has been the most widely used technique for rare earths separation. In this study, thermodynamics and kinetics of lutetium extraction with HEH(EHP) in hydrochloric acid medium were investigated. The extraction mechanism and the relevant parameters were determined by experiment research which can guide the practical extraction process. The data indicated that chloride ion had no effect on lutetium extraction, the rate constant increased when stirring speed was enhanced. Effects of temperature, HEH(EHP) concentration, acidity, and chloride concentration were also studied. Thickness of the diffusion film was also calculated to be 4.66×10~(–3) cm at 150 r/min.     

Effect of diluents on the extraction of praseodymium and samarium by Cyanex 923 from acidic nitrate medium

The solvent extraction of Pr(Ⅲ) and Sm(Ⅲ) with trialkyl phosphine oxide(Cyanex 923) in chloroform,carbon tetrachloride,n-octane,cyclohexane,1,2-dichloroethane,benzene,toluene,xylene and nitrobenzene from acidic nitrate medium was investigated.On the basis of slope analysis data,the composition of the extracted species was determined as(M(NO3)3?2CY923),CY923 refers to Cyanex 923.The values of the equilibrium constants and the separation factors were calculated.The effect of the diluents on the metal extracti...     

Green, orange, and red upconversion luminescence in Nd~(3 )/Yb~(3 ): Cs_2NaGdCl_6 powders under 785 nm laser excitation

Nd3 :Cs2NaGdCl6 and Nd3 , Yb3 :Cs2NaGdCl6 polycrystalline powder samples were prepared by Morss method E. Under 785 nm semiconductor laser pumping, the upconversion luminescence of Nd3 ions in Cs2NaGdCl6 was investigated at room temperature, and three upconversion emissions near 538 nm (Green), 603 nm (Orange), and 675 nm (Red) were observed and assigned to 4G7/2→4I9/2, (4G7/2→4I11/2; 4G5/2→4I9/2), and (4G7/2→4I13/2; 4G5/2→4I11/2), respectively. The dependences of these upconverted emissions on laser power and Nd3 ion concentration were investigated, to explore the upconversion mechanism. The effect of doping Yb3 ions on the upconversion luminescence of Nd3 in Cs2NaGdCl6 was also studied under 785 nm laser excitation. The energy transfer processes were discussed as the possible mecha-nism for the above upconversion emissions.     

Extraction of rare earth elements from their oxides using organophosphorus reagent complexes with HNO3 and H2O in supercritical CO2

Direct extraction of metals from solids with complexing agents in supercritical CO2(SC-CO2) has recently attracted interests in separation,purification,recovery,and analysis of metals.In the present study,the static/dynamic extraction of rare earth elements(Nd,Ce) from their oxides(Nd2O3,CeO2) with organophosphorus complexes with HNO3 and H2O in SC-CO2 was investigated.The static extraction efficiency of Nd from Nd2O3 with the tri-n-butylphosphate(TBP)-HNO3 complex could reach 95% under optimized experiment...     

Extraction Mechanism of La^3 ＋ from Hydrochloric Acid Solution Using Cyanex 302

The solvent extraction of La3 from hydrochloric acid solutions was investigated using bis (2, 4, 4-trimethylpentyl) monothiophosphinic acid (Cyanex 302, HL) as an extractant. The effect of .equilibrium of aqueous acidity on extraction of La^3 using Cyanex 302 in different diluents was discussed. The effects of extractant concentration and chloride ion on the extraction reaction were also studied. Stoichiometry of the extraction reactions and the nature of metal complexes formed were determined using slope analysis technique and IR measurement.     

Investigation of Coercivity Mechanism for Nd-Fe-B Magnets Prepared by Combination of Strip-Casting with Hydrogen Decrepitation Techniques

The coercivity mechanism of Nd-Fe-B magnets prepared by combination of strip-casting with hydrogen decrepi-tation techniques was investigated. The microstructure of (Nd0.935Dy0.065)14.5Fe79.4B6.1 magnet was observed. The average grain size is about 6 ～ 12 μm. The magnetizing field dependence of the hardmagnetic properties for the (Nd0.935Dy0.065)14.5 Fe79.4B6.1 and the temperature dependence of the coercivity for the Nd14.5Fe79.4B6.1 were investigated. Results show that the coereivity for magnets prepared by the combination of strip-casting with hydrogen decrepitation techniques is controlled by the nucleation mechanism.     

Electrochemical performance of La_(2–x)Sm_xMg_(16)Ni+200 wt.% Ni(x=0, 0.1, 0.2, 0.3, 0.4) alloys

Nanocrystalline and amorphous La_(2–x)Sm_xMg_(16)Ni+200wt.% Ni(x=0, 0.1, 0.2, 0.3, 0.4) alloys were prepared by mechanical milling technology. The structures of as-cast and milled alloys were investigated by X-ray diffraction(XRD), scanning electron microscopy(SEM) and transmission electron microscopy(TEM). Electrochemical performance of the alloy was studied by using an automatic galvanostatic system. The electrochemical impedance spectra(EIS) and Tafel polarization curves were measured by electrochemical workstation. The results indicated that the structures of the as-cast and milled alloys presented a multiphase structure with nanocrystalline and amorphous phase, moreover, transforming from nanocrystalline to amorphous phase with Sm doping. With the increase of Sm content, the maximum discharge capacity of the alloy was decreased from 922.6 to 649.1 m Ah/g, the high-rate discharge ability(HRD) was decreased, the cycle stability was strengthened, and the alloy exhibited excellent electrochemical kinetics. In addition, the charge-transfer resistance(R_(ct)) of alloy was lessened from 0.05874 to 0.02953 ? and the limiting current density(I_L) was descended from 2.08366 to 1.04592 A/g with increasing Sm content.     

Study on separation technology of Pr and Nd in D₂EHPA-HCl-LA coordination extraction system

The separation coefficient of Nd/Pr was lower in D2EHPA-HCl system. Pointing to this problem,the effect of the acidity of feed and the concentration of lactic acid on the distribution ratio,separation coefficient and extraction capacity was investigated in unsaponified D2EHPA-HCl-LA system,and the regression equations were calculated in this paper. The results showed that the distribution ratio and separation coefficient both increased with decreasing of feed acidity and increasing of the lactic acid concentration,and the extraction capacity increased with increasing of lactic acid concentration in D2EHPA-HCl-LA system. When the pH value of the feed was 3.5 and lactic acid concentration was 0.6 mol/L,the max separation coefficient was 1.57,and the extraction capacity was 27.87 g/L.     

Synthesis,crystal structures of novel complexes of rare earth with norfloxacin,interaction with DNA and BSA

Three novel rare earth complexes [N(CH 3) 4 ][Ln(NF) 4 ]·6H 2 O(Ln=Nd(III)(1),Sm(III)(2),Ho(III)(3)) were synthesized using hydrothermal method from norfloxacin HNF=1-ethyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-3-quinoline carboxylic acid,C 16 H 18 FN 3 O 3),imidazole and rare earth nitrates.The complexes were characterized by elemental analysis,FT-IR,TG-DTG and X-ray single crystal diffraction.Each rare earth ion was eight-coordinated with carboxyl-O atoms and keto-O atoms from norfloxacin.Four of the norfloxacin ions acted as bidentate chelate group took part in the coordination with rare earth ion.The structures of complexes were tetragonal system with space group I4 1 /acd,which were allomerism.The interaction between complex 1 and DNA was studied by electronic absorption spectra and fluorescence spectroscopy.The binding interaction between the complex 1 and bovine serum albumin(BSA) was studied by fluorescence spectroscopy.The complex 1 bound to DNA by the mode of partial intercalation.Complex 1 had a strong ability to quench the fluorescence from BSA.The complex interaction was mainly a static quenching process with BSA together with formation of two binding sites.     

Effect of loaded organic phase containing mixtures of silicon and aluminum, single iron on extraction of lanthanum in saponification P507-HCl system

Emulsification troubled normal extraction process of rare earths due to the existence of non-rare earth impurities,especially Si,Al and Fe.Against this background,the effect of emulsification caused by Si,Al and Fe on the La extraction with saponification P507(2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester) in chloride medium was systematically investigated.A series of experiments were carried out to study the relationship of the extraction capacity of La and the concentration of impurities.ZPM-203 polarizing microscope was applied to investigate the morphology of emulsification,and the cation exchange extraction mechanism of Fe and Al as well as La was clarified by IR spectra.The results showed that a low concentration of Si in organic phase would aggravate the emulsification with Al,and the formation of ME(micro emulsion) and club-shaped polymer would result in emulsification in the extraction of mixtures of Si and Al,single Fe,respectively.Furthermore,the accumulation of impurity such as Si,Al and Fe in the organic phase would severely reduce the extraction capacity of La simultaneously.     

New Methodological Approach to Investigation of Kinetics of REE Extraction in Nonstationary Conditions

The influence of periodical oscillations of the temperature on extraction and stripping processes in the extraction systems was studied. Two extraction systems were investigated： （1） 6 mol · L^-1 NaNO3-Nd（NO3）3-Pr（NO3）3-TBP kerosene and （2） [Nd（NO3）3 · 3TBP] -[ Pr（NO3）3 · 3TBP] -kerosene - 0.1 mol · L^-1 HNO3. Mathematical modeling of the nonstationary membrane extraction has been enhanced by including the dependence of the extraction rate constants on temperature. The values of activation energy for direct and reverse extraction and stripping reactions of Pr and Nd were calculated from experimental temporal dependencies of metal concentration and temperature by solving the reverse kinetics problem using the proposed mathematical model, A series of experiments with periodical oscillations of the temperature on the extraction system for the separation of rare earth elements （REE） using bulk liquid membrane between two extractors were performed. The mathematical model adequately describes the experimental data. The optimization of the extraction process for separation of REE by liquid membrane, under the influence of periodical oscillation of the temperature, was made based on the extraction rate constants and activation energies. The optimal conditions of separation by liquid membrane were found： frequency and amplitude of thermal oscillations, liquid membrane flow rate, and optimal ratio between organic and aqueous phase in extractors.     

Efficient extraction and stripping of Nd(Ⅲ),Eu(Ⅲ) and Er(Ⅲ) by membrane dispersion micro-extractors

The extraction of low concentration rare earth elements at high phase ratio was investigated. The traditional extraction set-up, such as mixer-settler, have drawbacks of easy emulsification, difficult separation and low efficiency if operated at the above condition. Membrane dispersion micro-extractor,owing to its well-dispersed, high surface-to-volume ratio and fast mass transfer rate, was employed in our work. Nd(Ⅲ),Eu(Ⅲ),Er(Ⅲ) were chosen to represent light, medium,heavy rare earth elements(REEs). The extraction process of REEs with 2-ethylhexyl phosphoric acid-2-ethylhexyl ester(P507) was investigated by membrane dispersion micro-extractors. Firstly, the extraction equilibrium of these three elements was explored in the stirred conical flasks, and it is indicated that the extraction efficiencies can be 0.95, 0.97 and 0.98, respectively within 40 min at phase ratio of 100:1. Then the effects of operational conditions such as the residence time, organic and aqueous flow rates on extraction efficiency were also explored in micro-extractors. The results indicate that the efficiency decreases and then increases if increasing aqueous phase flow rate, residence time and droplets' diameter are the key factors of this process. Increasing the phase ratio reduces the extraction efficiency significantly. When the REEs solution has an initial pH of 4.00, the flow rates of continuous and dispersed phase are 40 and 1.6 mL/min,respectively, and 90 mg/L Nd(Ⅲ), Eu(Ⅲ) and Er(Ⅲ) is extracted by 1 mol/L P507 at the out-let length of8 m. The extraction efficiencies are 0.978,0.983 and 0.991, respectively. Finally the stripping process was also studied with the micro-extractor. The stripping efficiencies of Nd(Ⅲ), Eu(Ⅲ) and Er(Ⅲ) can reach0.99, 0.96 and 0.91, respectively when the out-let length is 8 m and the concentration of hydrochloric acid is 1 mol/L. The developed approach offers a novel and simple strategy on the fast extraction and enrichment of low concentration rare earth elements from waste water.     

A novel method for synthesis of styryl phosphonate monoester and its application in La(Ⅲ) extraction

Herein,styryl phosphonate monoester(SPE) was synthesized and first introduced as rare earth extractant.The solvent extraction of lanthanum(Ⅲ) from nitrate solution using styryl phosphonate mono-isooctyl ester(SPE108),di-2-ethylhexyl phosphoric acid(D2 EHPA) and 2-ethylhexyl phosphonic acidmono-2-ethylhexyl ester(EHEHPA) as extractants was investigated.The effects of experimental parameters including equilibrium time,extractant concentration,aqueous pH,phase ratio and salt concentration on the extraction process were studied.The results indicate that the extraction ability and capacity of the extractants follow the order:SPE108 D2 EHPA EHEHPA.What's more,the extraction process is less affected by ammonium sulfate in the aqueous phase with SPE108.The results of the separation between lanthanum and adjacent lanthanides(Ce,Pr,Nd,Sm) show that SPE108 can separate lanthanides efficiently at low pH.The extraction mechanism of SPE108 is proved to be similar to D2 EHPA,and the density functional theory(DFT) calculation results infer that SPE108 exhibits superior extraction ability due to its strong electron-accepting ability.     

Solution and Thermodynamic Studies on Binary and Ternary Complexes of Lanthanides

The interactions of La(Ⅲ), Pr(Ⅲ), Nd(Ⅲ), Sm(Ⅲ), Eu(Ⅲ), Gd(Ⅲ), Dy(Ⅲ), and Yb(Ⅲ) with cytosine, 5-bromocytosine, 5-azacytosine and 5-flurocytosine as primary ligands (L) and guanine (A) as secondary ligand for both binary (1:1) as well as ternary (1:1:1) systems were investigated by potentiometric equilibrium measurements at 25, 35 and 45 ℃ in aqueous solution (ionic strength, μ=0.1 mol·dm-3 NaNO3). The stability constants of the binary (1:1) and ternary (1:1:1) metal-ligand complexes follow the following order La＜Pr＜Nd＜Sm＜Eu＞Gd＜Dy＞Yb. Results also indicate that the ternary lanthanide complexes of La(Ⅲ), Pr(Ⅲ), Nd(Ⅲ), Sm(Ⅲ), Eu(Ⅲ), Gd(Ⅲ), Dy(Ⅲ), and Yb(Ⅲ) are more stable than corresponding binary lanthanide complexes. The enthalpy (Δhof) and entropy (Δsof) changes for the formation of binary and ternary complexes were calculated from temperature coefficient data. The ΔΔSof values are positive for all the metal ligand systems. The negative ΔΔHof values indicate the extra stability of the ternary complexes by the exothermic enthalpy changes (ΔΔSof=ΔTSof-ΔBSof and ΔΔHof=ΔTHof-ΔBHof where ΔTSof, ΔTHof and ΔBSof, ΔBHof are the entropy and enthalpy values associated with the ternary and binary complexes, respectively). It was also proposed that the guanine is bonded to metal ions through N1/C6=O and N7 whereas cytosine and its derivatives are bonded through N3 atoms in ternary complexes.     

Extraction kinetics of neodymium from chloride medium using HEH/EHP saponified with magnesium bicarbonate solution

Magnesium bicarbonate solution is considered as an environmentally friendly extractant saponification agent for the solvent extraction of rare earth elements due to its advantage of minimum water pollution.In order to reveal the extraction regularity, optimize production-process and guide the use of this new extraction system, the extraction of Nd(Ⅲ) in chloride medium with HEH/EHP saponified by magnesium bicarbonate solution was investigated with the self-designed constant interfacial area cell. Besides, the effects of stirring rate, temperature, specific interfacial area and concentration of Mg-HEH/EHP on the extraction rate of Nd(Ⅲ) were systematically investigated. Results show that, the rate of extraction is governed by both diffusion and chemical reaction, and the extraction reaction takes place at the interface. The apparent activation energy of the extraction reaction is 16.88 kJ/mol. The corresponding rate equation is deduced. The mechanisms and rate-determining step are speculated based on interfacial reaction models, which is consistent with the experimental results.     

A preliminary study of polymer inclusion membrane for lutetium(Ⅲ)separation and membrane regeneration

This paper reports on the selective transport of Lu(Ⅲ) from La(III) and Sm(III) through a polymer inclusion membrane(PIM) composed of 40 wt% di(2-ethylhexyl) phosphinic acid(P227) and 60 wt%poly(vinylidene fluoride)(PVDF).Basically,the changes in surface morphology,thickness and water contact angle of this PVDF-based PIM containing P227(P227@PVDF PIM) with different polymer concentrations were investigated.By solvent extraction experiments,it is found that Lu(Ⅲ) can be selectively extracted from La(Ⅲ) and Sm(Ⅲ) at pH 1.5 in hydrochloric acid solution.According to this result,P227@PVDF PIM was used to selectively transport Lu(Ⅲ) from hydrochloric acid feed solution containing similar concentration of La(Ⅲ) and Sm(Ⅲ).The recovery factor of Lu(III) is 91% after 36 h,and about 5% of Sm(Ⅲ) was also transported through the PIM.The concentration of La(III) in the feed solution and the stripping solution does not change.Furthermore,to overcome the ubiquitous decline of transport efficiency caused by the loss of carrier or the damage of membrane structure after long-term use of PIMs,a process for regenerating PIMs was first proposed and implemented.By comparison of the regenerated PIM with the normal PIM,there is almost no difference in the SEM image,ATR-FTIR spectrum and Lu(III)transport efficiency.It is expected that P227@PVDF PIMs have the potential to be applied to the grouped separation of rare earth elements(REEs),and this study also can be as an inspiration for the further study on the PIMs regeneration process.